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Published on: April 15, 2013
Observation of Radical Rebound in a Mononuclear Nonheme Iron Model Complex
Thomas M Pangia1, Casey G Davies2, Joshua R Prendergast2,3
1Department of Chemistry , The Johns Hopkins University , Baltimore , Maryland 21218 , United States.
Abstract:
A nonheme iron(III) terminal methoxide complex, [FeIII(N3PyO2Ph)(OCH3)]ClO4, was synthesized. Reaction of this complex with the triphenylmethyl radical (Ph3C•) leads to formation of Ph3COCH3 and the one-electron-reduced iron(II) center, as seen by UV-vis, EPR, 1H NMR, and Mössbauer spectroscopy. These results indicate that homolytic Fe-O bond cleavage occurs together with C-O bond formation, providing a direct observation of the "radical rebound" process proposed for both biological and synthetic nonheme iron centers.
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